Oxidation pigment formation

Enough heat is generated by the reaction to keep the suspension at boiling point. It is essential to have an excess of iron metal to ensure complete decomposition of the nitrobenzene. The details of the reaction mechanism are not fully understood, but it is presumed that the nitrobenzene oxidizes Ee to Ee which is then hydrolysed. The acid is released by hydrolysis and pigment formation and dissolves the metallic iron and thus renews the supply of Ee " no additional acid other than that produced dur-... 

The type and quality of the pigment are determined not only by the nature and concentration of the additives, but also by the reaction rate. The rate depends on the grades of iron used, their particle size, the rates of addition of the iron and nitrobenzene (or another nitro compound), and the pH value. No bases are required to precipitate the iron compounds. Only ca. 3 % of the theoretical amount of acid is required to dissolve all of the iron. The aromatic nitro compound oxidizes the Fe2 + to Fe3 + ions, acid is liberated during hydrolysis and pigment formation, and more metallic iron is dissolved by the liberated acid to form iron(II) salts consequently, no additional acid is necessary. 

The formation of rutile mixed phases in the system Ti-Ni-Sb-0 is described in detail in [3.92], When nickel ions are to be included in the pigment and antimony trioxide is used to provide the antimony ions, oxygen must be present to ensure that nickel and antimony occupy the titanium sites in the lattice. If oxygen is excluded, only small amounts of nickel and antimony are taken up in solid solution, and no useful products are formed. The presence of oxidizing agents (e.g., nitrates) is necessary for the production of antimony-containing mixed metal oxide pigments. 

Eichner, K. The influence of water content on brown pigment formation in dehydrated foods and model systems and the inhibition of fat oxidation by browning intermediates, in Water Relations of Foods, Duckworth, R.B., Ed., Academic Press, New York, 1975, p. 417. 

Biosynthetic studies provided evidence that pigment formation involves the oxidative polymerization of cysteinyldopas of type 55CD (5-S-cysteinyldopa) via... 

Oxidations now known to be catalyzed by copper-containing enzymes were noticed over a century ago, when Schoenbein observed that oxidation of natural substrates resulted in pigment formation in mushrooms. Individual enzymes were gradually identified laccase by Yoshida in 1883 and tyrosinase by Bertrand in 1896. However, it was not imtil potato polyphenol oxidase was isolated in 1937 by Kubowitz that the role of copper was defined. The family of copper oxidases includes a number of enzymes of both plant and animal origin that may very probably be found to react through similar mechanisms, but which exhibit a number of individual characteristics. The enzymes to be described in this section include potato phenol oxidase, mushroom polyphenol oxidase (tyrosinase), laccase, mammalian and insect tyrosinase, and ascorbic acid oxidase. Each of these differs in certain respects from the others, and undoubtedly other related enzymes will be described from other sources that resemble these, but also display individualities. In these cases, identities in nomenclature must not be extended to imply identities in enzyme structure or activity. 

The series of reactions which bring about these changes in the cells are not known precisely. However, the studies of Lemberg, of Libowitzky and Fischer,of Siedel, Watson, and others have indicated the possible chemical pathway for bile pigment formation from heme. The process appears to be an oxidative one in which the heme apparently catalyzes its own destruction (Fig. 20). 

Metal oxide pigments (TiOj) are chemically Inert. Salts of weak acids (ZnS), however, enter into chemical reactions. The reaction products are more voluminous than the pigment Itself, thus facilitating crack formation and penetration Into the plastic. This reaction also results In optical changes. Figure 5.286. The homopolymer exhibits higher resistance to chemically active media diffusing into it than statistical copolymers [831]. 

H. Bile Pigment Formation and Heme-Catalyzed Oxidations. 195... 

Lead ll) oxide, PbO, exists in two forms as orange-red litharge and yellow massicot. Made by oxidation of Pb followed by rapid cooling (to avoid formation of Pb304). Used in accumulators and also in ceramics, pigments and insecticides. A normal hydroxide is not known but hydrolysis of lead(II) oxyacid salts gives polymeric cationic species, e.g. [Pb OfOH) ] and plumbates are formed with excess base. 

The examples in the preceding section, of the flotation of lead and copper ores by xanthates, was one in which chemical forces predominated in the adsorption of the collector. Flotation processes have been applied to a number of other minerals that are either ionic in type, such as potassium chloride, or are insoluble oxides such as quartz and iron oxide, or ink pigments [needed to be removed in waste paper processing [92]]. In the case of quartz, surfactants such as alkyl amines are used, and the situation is complicated by micelle formation (see next section), which can also occur in the adsorbed layer [93, 94]. 

Melanin Drying. One development (ca 1993) in hair coloring involves the formation of pigments within the hair that are very similar to natural melanin. Thus either catalytic or air oxidation of 5,6-dihydroxyindole [3131-52-0] can be effectively used to permanently dye hair within a short time (38). The formed color can, if required, be further modulated with dilute H2O2 or can be even totally removed from hair by this oxidant. 

Prussian Blue. Reaction of [Fe(CN)3] with an excess of aqueous h on(Ill) produces the finely divided, intensely blue precipitate Pmssian Blue [1403843-8] (tetrairon(Ill) tris(hexakiscyanoferrate)), Fe4[Fe(CN)3]. Pmssian Blue is identical to Turnbull s Blue, the name which originally was given to the material produced by reaction of [Fe(CN)3] with excess aqueous h on(Il). The soHd contains or has absorbed on its surface a large and variable number of water molecules, potassium ions (if present in the reaction), and h on(Ill) oxide. The h on(Il) centers are low spin and diamagnetic h on(Ill) centers are high spin. Variations of composition and properties result from variations in reaction conditions. Rapid precipitation in the presence of potassium ion affords a colloidal suspension of Pmssian Blue [25869-98-1] which has the approximate composition KFe[Fe(CN)3]. Pmssian Blue compounds are used as pigments in inks and paints and its formation on sensitized paper is utilized in the production of blueprints. 

Pigment Blue 1 [1325-87-7] 42595 2 triarylcarbonium PTMA salt (Victoria Blue B) condensation of 4,4 -bis-A/A/-dimethyl aminoben2ophenone with /V-ethyl-1-naphthylamine, followed by oxidation and salt formation... 

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